US11883801B2 - Steam reforming catalyst and fuel cell system using the same - Google Patents
Steam reforming catalyst and fuel cell system using the same Download PDFInfo
- Publication number
- US11883801B2 US11883801B2 US17/056,018 US201917056018A US11883801B2 US 11883801 B2 US11883801 B2 US 11883801B2 US 201917056018 A US201917056018 A US 201917056018A US 11883801 B2 US11883801 B2 US 11883801B2
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- United States
- Prior art keywords
- steam reforming
- reforming catalyst
- metal
- fuel cell
- anode
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 238000000629 steam reforming Methods 0.000 title claims abstract description 97
- 239000000446 fuel Substances 0.000 title claims description 70
- 229910052751 metal Inorganic materials 0.000 claims abstract description 104
- 239000002184 metal Substances 0.000 claims abstract description 104
- 239000007789 gas Substances 0.000 claims abstract description 38
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
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- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1247—Higher hydrocarbons
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present disclosure relates to a steam reforming catalyst and a fuel cell system.
- hydrogen which is a fuel supplied to an anode of a solid oxide fuel cell (SOFC)
- SOFC solid oxide fuel cell
- a steam reforming reaction is an endothermic reaction, additional heating by an external heat source is necessary in order to maintain a reaction temperature at which high catalytic activity is exhibited.
- autothermal steam reforming in which the steam reforming reaction is combined with a partial oxidation reaction, which is an exothermic reaction, has been studied.
- Patent Literature 1 discloses an autothermal reforming catalyst formed of a zirconia carrier supporting ruthenium or an inorganic oxide carrier (for example, alumina) supporting ruthenium and zirconium.
- Patent Literature 2 discloses a method for operating an oxidation autothermal reforming apparatus for producing a reformed gas that contains hydrogen as a main component by a reforming reaction using, as raw materials, a hydrocarbon or an aliphatic alcohol, steam, and an oxidizing gas, in which when an amount of reformed gas produced is increased, an operating condition is changed in the following order: first, the amount of the steam supplied is increased, subsequently, the amount the oxidizing gas supplied is increased, and finally, the amount of the hydrocarbon or the aliphatic alcohol supplied is increased.
- An aspect of the present disclosure relates to a steam reforming catalyst that promotes production of hydrogen from a gas containing a hydrocarbon in the presence of steam, the steam reforming catalyst including a carrier, and two or more catalyst metals supported on the carrier and including a first metal and a second metal, in which the first metal includes Ni, the second metal includes at least one of Co and Ru, and the carrier is represented by LaNbO 4 or La 1-x Sr x NbO 4 where x is in a range of 0 ⁇ x ⁇ 0.12.
- Another aspect of the present disclosure relates to a fuel cell system including
- FIG. 1 is a schematic view illustrating the configuration of a fuel cell system according to an embodiment of the present disclosure.
- FIG. 2 is a schematic sectional view illustrating a fuel cell used in a fuel cell system according to an embodiment of the present disclosure.
- FIG. 3 is a schematic sectional view illustrating a cell structure included in the fuel cell in FIG. 2 .
- FIG. 4 is a graph showing an autothermal steam reforming performance of catalysts in which Ni is supported on a La 1-x Sr x NbO 4 (0 ⁇ x ⁇ 0.3) carrier.
- the steam reforming is performed at a high temperature of about 700° C. or higher. However, at a lower reaction temperature of steam reforming, the energy consumed by an external heat source can be reduced. Furthermore, the reaction temperature of a steam reformer that is used for supplying hydrogen used in a SOFC is preferably substantially the same as an operating temperature of the SOFC. Accordingly, in the case of combination with a SOFC that operates in an intermediate temperature range of 400° C. or higher and 600° C. or lower, the steam reforming reaction is preferably allowed to proceed at a temperature of 400° C. or higher and 600° C. or lower, which is the same as the operating temperature of the SOFC.
- reaction temperature of the steam reformer cannot be decreased because reactivity of a catalyst used in the steam reforming reaction is not sufficient at a temperature of lower than 700° C.
- a steam reforming catalyst is a steam reforming catalyst that promotes production of hydrogen from a gas containing a hydrocarbon in the presence of steam, the steam reforming catalyst including:
- the catalyst in which catalyst metals including Ni as a first metal and Co and/or Ru as a second metal are supported on LaNbO 4 or La 1-x Sr x NbO 4 (0 ⁇ x ⁇ 0,12) serving as a carrier has high catalytic activity in the steam reforming reaction even at intermediate to low temperatures of lower than 700° C.
- This catalyst enables steam reforming to be performed at 600° C. or lower and can reduce the amount of energy consumption necessary to heat a steam reformer to higher than 600° C.
- the carrier is preferably formed of La 1-x Sr x NbO 4 where x is in a range of 0.08 ⁇ x ⁇ 0.12.
- x is in a range of 0.08 ⁇ x ⁇ 0.12.
- methane (CH 4 ), carbon dioxide (CO 2 ), carbon monoxide (CO), and carbon (C) can be produced as by-products.
- carbon may adhere to the surface of the reforming catalyst as soot and cause a decrease in the reaction efficiency.
- the amount of methane produced can also be reduced.
- the second metal preferably includes at least Co, in this case, a conversion rate from the hydrocarbon to hydrogen can be increased.
- the catalyst metals may further include a third metal different from Ni and the second metal.
- a content of the catalyst metals is preferably 1% by mass or more and 5% by mass or less based on a whole mass of the catalyst metals and the carrier.
- a content of the second metal is preferably 0.15% by mass or more and 0.5% by mass or less based on a total mass of the catalyst metals and the carrier. In this case, a high conversion rate from the hydrocarbon can be obtained while the amount of carbon produced is maintained to be low.
- a high conversion rate can be obtained by setting the content of the second metal to 0.25% by mass or more and 0.35% by mass or less based on the total mass of the catalyst metals and the carrier.
- the carrier is preferably supported on a porous body.
- the carrier is supported on surfaces of pores of the porous body, the area of surfaces where the hydrocarbon gas comes in contact with the catalyst metals can be increased to improve the reaction efficiency.
- the carrier is supported on a porous body having a honeycomb structure.
- the hydrocarbon preferably includes propane.
- the steam reforming catalyst is particularly good in term of steam reforming of propane.
- the gas containing a hydrocarbon is preferably a mixed gas containing the hydrocarbon and oxygen.
- the steam reforming catalyst exhibits good catalytic activity under autothermal conditions.
- a fuel cell system includes a fuel cell that includes a cell structure including a cathode, an anode, and a solid electrolyte layer disposed between the cathode and the anode, a cathode-side separator disposed on a cathode side with respect to the solid electrolyte layer, an anode-side separator disposed on an anode side with respect to the solid electrolyte layer, an oxidant channel which is formed between the cathode-side separator and the cathode and through which an oxidant is supplied to the cathode, and a fuel channel which is formed between the anode-side separator and the anode and through which a fuel is supplied to the anode; and a steam reformer.
- the steam reformer includes the steam reforming catalyst described above. According to the fuel cell system, steam reforming can be performed at a relatively low temperature of 600° C. or lower. Thus, energy consumed by an external heat source can be reduced, and the fuel cell can be operated at high efficiency.
- an operating temperature of the fuel cell and a reaction temperature of the steam reformer are each 400° C. or higher and 600° C. or lower. Since the temperature difference between the reaction temperature of steam reforming and the operating temperature of the SOFC can be reduced, heat loss can be reduced when a reformed gas is supplied to the fuel cell, and the energy efficiency of the fuel cell can be further increased.
- a steam reforming catalyst is constituted by supporting two or more catalyst metals including a first metal and a second metal on LaNhO 4 or La 1-x Sr x NbO 4 serving as a carrier.
- x is in a range of 0 ⁇ x ⁇ 0.12.
- the first metal includes, for example, Ni.
- the second metal includes, for example, at least one of Co and Ru.
- the LaNbO 4 or La 1-x Sr x NbO 4 can be synthesized by a solid-phase method such as a solid-phase synthesis method. Specifically, in the case of using a solid-phase synthesis method, the synthesis can be performed by, for example, mixing La 2 O 3 , Nb 2 O 5 , and SrO and heat-treating the mixture. Alternatively, a liquid-phase method may be employed, and the synthesis may be performed by sintering.
- the first metal and the second metal can be supported on the carrier by using, for example, an evaporation drying method.
- a salt compound of the first metal for example, nickel(II) nitrate hexahydrate (Ni(NO 3 ) 2.6 6H 2 O) can be used.
- a salt compound of the second metal for example, cobalt(II) nitrate hexahydrate (Co(NO 3 ) 2 ; 6H 2 O) can be used as a Co source, or ruthenium(III) trinitrate (Ru(NO 3 ) 3 ) can be used as a Ru source.
- a surface of a carrier is brought into contact with a solution in which the first metal source and the second metal source are dissolved, and the solvent is then removed by the evaporation drying method to support the compound of the first metal and the compound of the second metal on the carrier.
- the solvent is then removed by the evaporation drying method to support the compound of the first metal and the compound of the second metal on the carrier.
- nickel nitrate and cobalt nitrate or ruthenium nitrate
- nitric acid is removed by heat treatment (for example, at 600° C.) in a reducing atmosphere, and the first metal and the second metal are supported on the carrier.
- the amounts of the first metal and the second metal supported on the carrier can be evaluated by inductively coupled plasma (ICP) emission spectroscopy.
- ICP inductively coupled plasma
- a steam reformer includes a reforming unit (not illustrated) provided with a steam reforming catalyst and a heating unit (not illustrated) configured to heat the reforming unit.
- the reforming unit includes a porous body, and the steam reforming catalyst is supported on surfaces of pores of the porous body.
- the porous body porous material
- examples of the porous body include aluminum oxide (alumina), zirconium oxide (zirconia), and cordierite (2MgO ⁇ 2Al 2 O 3 ⁇ 5SiO 2 ).
- the porous body is preferably one having a honeycomb structure.
- Such a porous body having a honeycomb structure is produced by, for example, kneading a powder of a porous material (optionally with a binder), and forming the kneaded product into a predetermined shape by, for example, extrusion molding.
- the steam reforming catalyst supported on the porous body promotes the steam reforming reaction of the hydrocarbon to produce hydrogen gas from the gas containing the hydrocarbon and steam.
- a reformed gas containing hydrogen gas and containing by-products of the steam reforming reaction such as methane, carbon dioxide, and carbon monoxide is obtained.
- the reformed gas containing hydrogen gas is supplied to a fuel cell described later.
- the hydrogen gas is separated from the reformed gas by using, for example, a hydrogen permeable film, and the hydrogen gas after separation can be supplied to the fuel cell.
- a cylindrical steam reformer can be used.
- Such a cylindrical steam reformer has two treatment chambers in an inner cylindrical section and an outer cylindrical section located on the outer peripheral side of an inner cylindrical section.
- the inner cylindrical section and the outer cylindrical section are partitioned by a porous body.
- a gas containing a hydrocarbon and steam is supplied to one of the inner cylindrical section and the outer cylindrical section.
- the gas containing the hydrocarbon and steam passes through pores of the porous body and flows into the other one of the inner cylindrical section and the outer cylindrical section.
- the hydrocarbon is subjected to steam reforming by the action of a steam reforming catalyst supported on the porous body, and a reformed gas can be taken from the other one of the inner cylindrical section and the outer cylindrical section.
- FIG. 1 schematically illustrates the configuration of a fuel cell system according to an embodiment of the present disclosure.
- a fuel cell system 60 includes at least a steam reformer 61 and a fuel cell 10 .
- the steam reformer 61 the steam reformer described above is used.
- a gas 62 containing a hydrocarbon and steam is supplied to the steam reformer 61 , and hydrogen gas is produced.
- a reformed gas (fuel gas) 63 containing this hydrogen gas is supplied to the fuel cell 10 .
- air (oxidant) 64 is also supplied to the fuel cell 10 .
- An exhaust gas 65 is discharged from the fuel cell 10 .
- FIG. 2 is a schematic sectional view illustrating a fuel cell (solid oxide fuel cell) used in combination with a steam reformer.
- a fuel cell 10 includes a cell structure 1 .
- FIG. 3 illustrates an example of a schematic sectional view of the cell structure 1 .
- the cell structure 1 includes a cathode 2 , an anode 3 , and a solid electrolyte layer 4 disposed therebetween.
- the anode 3 and the solid electrolyte layer 4 are combined to form an electrolyte layer-electrode assembly 5 .
- the fuel cell 10 includes, in addition to the cell structure 1 , an oxidant channel 23 through which an oxidant is supplied to the cathode 2 , a fuel channel 53 through which a fuel is supplied to the anode 3 , a cathode-side separator 22 , and an anode-side separator 52 .
- the oxidant channel 23 is formed by the cathode-side separator 22
- the fuel channel 53 is formed by the anode-side separator 52 .
- the cell structure 1 is sandwiched between the cathode-side separator 22 and the anode-side separator 52 .
- the oxidant channel 23 of the cathode-side separator 22 is disposed so as to face the cathode 2 of the cell structure 1
- the fuel channel 53 of the anode-side separator 52 is disposed so as to face of the anode 3 .
- a solid electrolyte that exhibits proton conductivity or oxygen ion conductivity in an intermediate temperature range of 400° C. or higher and 600° C. or lower is used as the solid electrolyte layer.
- a perovskite oxide such as BaCe 0.8 Y 0.2 O 2.9 (BCY) or BaZr 0.8 Y 0.2 O 2.9 (BZY) exhibits high proton conductivity in the intermediate temperature range and thus can be used as a solid electrolyte of an intermediate temperature fuel cell.
- BCY BaCe 0.8 Y 0.2 O 2.9
- BZY BaZr 0.8 Y 0.2 O 2.9
- These solid electrolytes can be formed by, for example, sintering.
- the thickness of the solid electrolyte layer is, for example, 1 ⁇ m or more and 50 ⁇ m or less, and preferably 3 ⁇ m or more and 20 ⁇ m or less. A thickness of the solid electrolyte layer within such a range is preferred because the resistance of the solid electrolyte layer is suppressed to be low.
- the solid electrolyte layer forms a cell structure together with a cathode and an anode and can be incorporated in a fuel cell.
- the solid electrolyte layer is sandwiched between the cathode and the anode, one main surface of the solid electrolyte layer is in contact with the anode, and the other main surface is in contact with the cathode.
- the cathode has a porous structure.
- a reaction between protons conducted through the solid electrolyte layer and oxide ions proceeds.
- the oxide ions are produced by the dissociation of an oxidant (oxygen) introduced through the oxidant channel.
- the material of the cathode is preferably, for example, compounds containing lanthanum and having a perovskite structure (such as ferrite, manganite, and/or cobaltite). Of these compounds, compounds further containing strontium are more preferred.
- the cathode may include a catalyst such as Pt. When the catalyst is included, the cathode can be formed by mixing the catalyst with the above material and sintering the mixture.
- the cathode can be formed by, for example, sintering a raw material of the above material.
- a binder, an additive, and/or a dispersion medium may be used together with the raw material, as needed.
- the thickness of the cathode is not particularly limited, but can be appropriately determined from, for example, 5 ⁇ m or more and 2 mm or less, and may be about 5 ⁇ m or more and about 40 ⁇ m or less.
- the anode has a porous structure. At the anode, a reaction of oxidizing a fuel, such as hydrogen, introduced through the fuel channel and releasing protons and electrons (oxidation reaction of fuel) proceeds.
- a reaction of oxidizing a fuel such as hydrogen
- the material of the anode publicly known materials can be used.
- the material of the anode include composite oxides of nickel oxide (NiO) serving as a catalyst component and a proton conductor (such as yttrium oxide (Y 2 O 3 ), BCY, or BZY).
- the anode can be formed by, for example, sintering raw materials.
- the anode can be formed by sintering a mixture of a NiO powder and a powder of a proton conductor or the like.
- the thickness of the anode can be appropriately determined from, for example, 10 ⁇ m or more and 2 mm or less and may be 10 ⁇ m or more and 100 ⁇ m or less.
- the thickness of the anode 3 is larger than that of the cathode 2 , and the anode 3 functions as a support that supports the solid electrolyte layer 4 (by extension, the cell structure 1 ).
- the thickness of the anode 3 need not necessarily be larger than that of the cathode 2 .
- the thickness of the anode 3 may be substantially the same as the thickness of the cathode 2 .
- the structure is not limited to this case.
- the cathode and the solid electrolyte layer may be combined to form an electrolyte layer-electrode assembly.
- the oxidant channel 23 has an oxidant inlet into which the oxidant flows and an oxidant outlet through which, for example, water produced by the reaction and an unused oxidant are discharged (both not illustrated).
- An example of the oxidant is a gas containing oxygen.
- the fuel channel 53 has a fuel-gas inlet into which a fuel gas flows and a fuel-gas outlet through which, for example, an unused fuel and H 2 O, N 2 , and CO 2 formed by the reaction are discharged (both not illustrated).
- the fuel gas include gases containing a gas of hydrogen, methane, ammonia, carbon monoxide, or the like.
- the fuel cell 10 may include a cathode-side current collector 21 disposed between the cathode 2 and the cathode-side separator 22 and an anode-side current collector 51 disposed between the anode 3 and the anode-side separator 52 .
- the cathode-side current collector 21 has a function of collecting a current and a function of diffusively supplying an oxidant introduced through the oxidant channel 23 to the cathode 2 .
- the anode-side current collector 51 has a function of collecting a current and a function of diffusively supplying a fuel gas introduced through the fuel channel 53 to the anode 3 . Therefore, the current collectors are each preferably a structure having sufficient air-permeability. In the fuel cell 10 , the current collectors 21 and Si need not necessarily be provided.
- the fuel cell 10 includes a proton conductive solid electrolyte
- the fuel cell 10 can be operated at lower than 700° C., and preferably in an intermediate temperature range of about 400° C. or higher and about 600° C. or lower.
- the cell structure 1 In the case where a plurality of cell structures are stacked to form a fuel cell, for example, the cell structure 1 , the cathode-side separator 22 , and the anode-side separator 52 are stacked as a unit.
- the plurality of cell structures 1 may be connected together in series with, for example, a separator that includes gas channels (an oxidant channel and a fuel channel) in both surfaces thereof.
- heat-resistant alloys such as stainless steels, nickel-based alloys, and chromium-based alloys can be exemplified in terms of proton conductivity and heat resistance.
- stainless steels are preferred in view of their low cost.
- the operating temperatures of protonic ceramic fuel cells (PCFCs) are about 400° C. or higher and about 600° C. or lower, and thus stainless steels can be used as the materials of the separators.
- Examples of the structure used as each of the cathode-side current collector and the anode-side current collector include porous metal bodies, metal meshes, perforated metals, and expanded metals that contain, for example, silver, silver alloys, nickel, and nickel alloys.
- porous metal bodies are preferred in terms of lightweight properties and air-permeability.
- porous metal bodies having a three-dimensional mesh-like structure are preferred.
- the three-dimensional mesh-like structure refers to a structure in which rod-like or fibrous metals constituting a porous metal body are three-dimensionally connected together to form a network. Examples thereof include sponge-like structures and nonwoven fabric-like structures.
- the porous metal body can be formed by, for example, coating a resin porous body having continuous pores with the metal described above. After the metal coating treatment, the inner resin is removed. As a result, a hollow space is formed inside the skeleton of the porous metal body, and the skeleton becomes hollow.
- a resin porous body having continuous pores with the metal described above.
- the inner resin is removed.
- a hollow space is formed inside the skeleton of the porous metal body, and the skeleton becomes hollow.
- “Celmet” formed of nickel and manufactured by Sumitomo Electric Industries, Ltd. can be used as a commercially available porous metal body having the above structure.
- the fuel cell can be manufactured by a publicly known method except that the cell structure described above is used.
- a La 2 O 3 powder and a Nb 2 O 5 powder were mixed in a ball mill and disintegrated. Subsequently, the disintegrated product was calcined at 800° C. for 10 hours in an air atmosphere and then disintegrated again. Subsequently, the disintegrated product was heat-treated at 1,200° C. for 10 hours to synthesize LaNbO 4 .
- the LaNhO 4 prepared as described above was immersed in an aqueous nickel(II) nitrate solution, and water was then removed by the evaporation drying method. At this time, the Ni concentration in the aqueous nickel nitrate solution was adjusted such that the Ni content after removal of water became 3% by mass based on the total mass of LaNbO 4 and Ni.
- the resulting product was screened with a sieve having 30 meshes per 1 inch and heat-treated in an atmosphere containing hydrogen at 600° C. for one hour to prepare a steam reforming catalyst a1.
- the steam reforming catalyst a1 (0.1 g) was placed between quartz wool wads and fixed in a reaction tube. Next, the reaction tube in which the steam reforming catalyst a1 was placed was heated to 550° C.
- a mixed gas of C 3 H 8 :O 2 :H 2 O:N 2 was introduced into the reaction tube such that the flow rates became 6.82 cc/min:1.19 cc/min:65.1 cc/min:59.5 cc/min, respectively.
- the gas composition after the reaction was analyzed by gas chromatography (apparatus name: Agilent 7890) in which a TCD and an FID were used in combination.
- the masses of C 3 H 8 , H 2 O, H 2 , CH 4 , CO 2 , and CO contained in the gas after the reaction (reformed gas) were determined, and the sum of the masses was calculated.
- the sum of the masses was subtracted from the total mass of C 3 H 8 , H 2 O, and O 2 contained in the gas before the reaction (supply gas). The mass remaining after the subtraction was determined as an amount of C (carbon) produced after the reaction.
- the C 3 H 8 conversion rate (%), the rate of H 2 production ( ⁇ mol/min), and the selectivity and yield (%) of CH 4 , CO 2 , CO, and C were determined and evaluated.
- FIG. 4 shows the evaluation results of the conversion rate and the yield.
- the steam reforming catalyst a1 corresponds to the catalyst in which the amount of Sr added is 0% in FIG. 4 .
- the amount of Sr added means a percentage % of the number of atoms of St Sr that replaces La in a La 1-x Sr x NbO 4 carrier and refers to a numerical value obtained by multiplying x by 100.
- La 1-x Sr x NbO 4 was synthesized by the same method as in Reference Example 1 except that a La 2 O 3 powder, a Nb 2 O 5 powder, and a SrO powder were mixed in a ball mill and a disintegrated product obtained by disintegration was calcined.
- a plurality of La 1-x Sr x NbO 4 carriers having different amounts of Sr added were prepared, and Ni was supported on each of the carriers by the same method as in Reference Example 1 to prepare steam reforming catalysts a2 to a4.
- the C 3 H 8 conversion rate tends to decrease with the addition of Sr.
- the yield of C (carbon) significantly decreased.
- the steam reforming catalyst a2 although the C 3 H 8 conversion rate is lower than that of the steam reforming catalyst a1, the steam reforming catalyst a2 maintains a high rate of H 2 production that is substantially equal to that of the steam reforming catalyst a1 to which Sr is not added. This means that, in the steam reforming catalyst a2, H 2 is preferentially produced compared with the steam reforming catalyst a1.
- the effect of preferentially producing 142 and the effect of reducing the amount of C produced can be similarly achieved when the amount of Sr added is 8% or more and 12% or less (0,08 ⁇ 0.12).
- a La 0.9 Sr 0.1 NbO 4 carrier was synthesized as in the steam reforming catalyst a2 of Reference Example 2, and steam reforming catalysts containing Ni and a second metal (Co, Ru, Cu, Fe, Pd, or Pt) as catalyst metals were prepared.
- Co and Ru are Examples.
- Cu, Fe, Pd, and Pt are Reference Examples.
- the second metal was supported on the La 0.9 Sr 0.1 NbO 4 carrier by the evaporation drying method as in Ni.
- Ni nickel( 11 ) nitrate hexahydrate was used.
- a compound of the second metal with regard to Co, Ru, Cu, Fe, and Pd, a nitrate or a hydrate of a nitrate was used.
- Pt chloroplatinic acid (hexachloroplatinic(1V) acid hexahydrate) was used.
- the Ni compound and the compound of the second metal were dissolved in water in a predetermined blending ratio, and La 0.9 Sr 0.1 NbO 4 was immersed in the aqueous solution of the Ni compound and the second metal. Subsequently, the aqueous solution in a glass container was heated at 85° C. while being stirred with a stirrer to thereby evaporate water. At this time, the concentrations of the Ni compound and the second metal compound contained in the aqueous solution were adjusted such that the total content of Ni. and the second metal after removal of water became 3% by mass based on the total mass of La 0.9 Sr 0.1 NbO 4 , Ni, and the second metal.
- the blending ratio of the Ni compound and the compound of the second metal was adjusted such that the ratio of the second metal to the total of Ni and the second metal contained in the compounds became 10% by mass. Accordingly, the proportion of the second metal with respect to the whole of the steam reforming catalyst after removal of water becomes 0.3% by mass.
- the resulting products were each screened with a sieve having 30 meshes per 1 inch and heat-treated in an atmosphere containing hydrogen at 600° C. for one hour to prepare a steam reforming catalyst b1 containing Co as the second metal, a steam reforming catalyst c1 containing Ru as the second metal, a steam reforming catalyst d1 containing Cu as the second metal, a steam reforming catalyst e1 containing Fe as the second metal, a steam reforming catalyst f1 containing Pd as the second metal, and a steam reforming catalyst a1 containing Pt as the second metal.
- the C 3 H 8 conversion rate (%), the rate of 1:12 production ( ⁇ mol/min), and the selectivity (%) of CH 4 , CO 2 , CO, and C of each of the steam reforming catalysts b1, c1, d1, e1, f1, and g1 were determined by the same method as in Reference Example 1. Table 1 shows the evaluation results.
- Catalyst metals containing Ni and Co were supported on a La 0.9 Sr 0.1 NbO 4 carrier as in the steam reforming catalyst b1 of Example 3. At this time, the blending ratio of Ni and Co was changed while the total mass of Ni and Co relative to the total mass of La 0.9 Sr 0.1 NbO 4 . Ni, and Co was constant (3% by mass).
- the C 3 H 8 conversion rate (%), the rate of H 2 production ( ⁇ mol/min), and the selectivity (%) of CH 4 , CO 2 , CO, and C of each of the steam reforming catalysts b2 and b3 were determined by the same method as in Example 1.
- Table 2 shows the evaluation results.
- Table 2 also shows the results (that are the same as those in Table 1) of the catalyst a2 in which Co is not supported and the catalyst b1 in which Co is supported in an amount of 0.3% by mass.
- the steam reforming catalyst b1 containing Ni and Co as catalyst metals and the steam reforming catalyst c1 containing Ni and Ru as catalyst metals exhibited C 3 H 8 conversion rates that were higher than the C 3 H 8 conversion rate of the steam reforming catalyst a2 containing Ni alone as a catalyst metal. In addition, the production of C (carbon) is also suppressed.
- the selectivity of C (carbon) is a negative value. This is because the amount of C (carbon) produced is determined by a subtraction on the basis of the results of analysis by gas chromatography, as described above. It was found that, in the steam reforming catalyst c1, the amount of C (carbon) produced was within the range of measurement error, and C (carbon) was hardly produced, Although the steam reforming catalyst e1 is inferior to the steam reforming catalyst b1 in terms of the C 3 H 8 conversion rate, the steam reforming catalyst c1 is superior to the steam reforming catalyst b1 in that the production of C (carbon) hardly occurs.
- Tables 1 and 2 the numerical values in the parentheses in the selectivity of CH 4 , CO 2 , CO, and C each indicate an amount (%) of change in the selectivity from that of the steam reforming catalyst a2 and represent how much the selectivity is changed by changing a catalyst metal in the case where the carrier is the same.
- the amount of C (carbon) produced is larger than that in the steam reforming catalyst a2.
- the results in Tables 1 and 2 show that, even in the case where LaNbO 4 is used as a carrier, the yield of C (carbon) can be reduced by using Co or Ru as the second metal.
- the steam reforming catalyst a1 in which LaNbO 4 containing no Sr is used as a carrier has a better C 3 H 8 conversion rate than that of the steam reforming catalyst a2. Accordingly, a steam reforming catalyst in which Ni and at least one of Ru and Co are supported as catalyst metals on a LaNbO 4 carrier enables the amount of C (carbon) produced to be significantly reduced while maintaining a high C 3 H 8 conversion rate.
- the amount of Co supported is preferably within a range of a value close to 0.15% by mass (for example, 0,1% by mass or more and 0,2% by mass or less) or a range of a value close to 0.5% by mass (for example, in a range of 0.45% by mass or more and 0.55% by mass or less) from the viewpoint of reducing the amount of C (carbon) produced.
- the carrier is formed of La 1-x Sr x NbO 4 to which Sr is added, as long as x is within a range of 0 ⁇ x ⁇ 0.12, the amount of C (carbon) produced can be significantly reduced by using Ni and at least one of Ru and Co as catalyst metals while a high C 3 H 8 conversion rate is maintained.
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CN112313007A (zh) | 2021-02-02 |
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EP3815782A1 (fr) | 2021-05-05 |
JP7173142B2 (ja) | 2022-11-16 |
US20210213430A1 (en) | 2021-07-15 |
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CN112313007B (zh) | 2023-05-05 |
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